CN102614894B - Supported catalyst used for synthesis of diisopropylamine from isopropylamine and preparation method as well as application of supported catalyst - Google Patents
Supported catalyst used for synthesis of diisopropylamine from isopropylamine and preparation method as well as application of supported catalyst Download PDFInfo
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- CN102614894B CN102614894B CN2012100545324A CN201210054532A CN102614894B CN 102614894 B CN102614894 B CN 102614894B CN 2012100545324 A CN2012100545324 A CN 2012100545324A CN 201210054532 A CN201210054532 A CN 201210054532A CN 102614894 B CN102614894 B CN 102614894B
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- isopropylamine
- diisopropylamine
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- UAOMVDZJSHZZME-UHFFFAOYSA-N diisopropylamine Chemical compound CC(C)NC(C)C UAOMVDZJSHZZME-UHFFFAOYSA-N 0.000 title claims abstract description 123
- 239000003054 catalyst Substances 0.000 title claims abstract description 89
- 229940043279 diisopropylamine Drugs 0.000 title claims abstract description 41
- JJWLVOIRVHMVIS-UHFFFAOYSA-N isopropylamine Chemical compound CC(C)N JJWLVOIRVHMVIS-UHFFFAOYSA-N 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 230000015572 biosynthetic process Effects 0.000 title abstract description 5
- 238000003786 synthesis reaction Methods 0.000 title abstract description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 39
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 39
- 229910052802 copper Inorganic materials 0.000 claims abstract description 20
- 239000010949 copper Substances 0.000 claims abstract description 20
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 20
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 20
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 19
- 238000000034 method Methods 0.000 claims abstract description 14
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000006243 chemical reaction Methods 0.000 claims description 27
- 230000004913 activation Effects 0.000 claims description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- 238000011068 loading method Methods 0.000 claims description 12
- 238000007598 dipping method Methods 0.000 claims description 10
- 239000007788 liquid Substances 0.000 claims description 10
- 239000011148 porous material Substances 0.000 claims description 10
- 239000000706 filtrate Substances 0.000 claims description 9
- 229910052739 hydrogen Inorganic materials 0.000 claims description 9
- 239000001257 hydrogen Substances 0.000 claims description 9
- 239000000463 material Substances 0.000 claims description 9
- 206010013786 Dry skin Diseases 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 8
- 150000002815 nickel Chemical class 0.000 claims description 8
- 150000003057 platinum Chemical class 0.000 claims description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 6
- 230000000694 effects Effects 0.000 claims description 6
- 239000011259 mixed solution Substances 0.000 claims description 6
- NWAHZABTSDUXMJ-UHFFFAOYSA-N platinum(2+);dinitrate Chemical group [Pt+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O NWAHZABTSDUXMJ-UHFFFAOYSA-N 0.000 claims description 6
- 239000000047 product Substances 0.000 claims description 6
- 239000007787 solid Substances 0.000 claims description 6
- 238000009423 ventilation Methods 0.000 claims description 6
- 238000009833 condensation Methods 0.000 claims description 4
- 230000005494 condensation Effects 0.000 claims description 4
- 238000004821 distillation Methods 0.000 claims description 4
- 235000015895 biscuits Nutrition 0.000 claims description 3
- 238000010304 firing Methods 0.000 claims description 3
- -1 hydrogen amine Chemical class 0.000 claims description 3
- 238000005070 sampling Methods 0.000 claims description 3
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 2
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical group [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 2
- 238000009834 vaporization Methods 0.000 claims description 2
- 230000008016 vaporization Effects 0.000 claims description 2
- 230000008569 process Effects 0.000 abstract description 6
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 239000004480 active ingredient Substances 0.000 abstract 2
- 230000002194 synthesizing effect Effects 0.000 abstract 2
- 238000007323 disproportionation reaction Methods 0.000 abstract 1
- 238000009776 industrial production Methods 0.000 abstract 1
- 231100000053 low toxicity Toxicity 0.000 abstract 1
- 229910003158 γ-Al2O3 Inorganic materials 0.000 abstract 1
- 238000002474 experimental method Methods 0.000 description 7
- JYIMWRSJCRRYNK-UHFFFAOYSA-N dialuminum;disodium;oxygen(2-);silicon(4+);hydrate Chemical compound O.[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[Na+].[Na+].[Al+3].[Al+3].[Si+4] JYIMWRSJCRRYNK-UHFFFAOYSA-N 0.000 description 6
- 230000008859 change Effects 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- SXTLQDJHRPXDSB-UHFFFAOYSA-N copper;dinitrate;trihydrate Chemical compound O.O.O.[Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O SXTLQDJHRPXDSB-UHFFFAOYSA-N 0.000 description 4
- SPIFDSWFDKNERT-UHFFFAOYSA-N nickel;hydrate Chemical compound O.[Ni] SPIFDSWFDKNERT-UHFFFAOYSA-N 0.000 description 4
- 239000012153 distilled water Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000006200 vaporizer Substances 0.000 description 3
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 2
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 2
- 229910021536 Zeolite Inorganic materials 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- KGCZCJMWEGKYMC-UHFFFAOYSA-N [Ni].[Cu].[Pt] Chemical compound [Ni].[Cu].[Pt] KGCZCJMWEGKYMC-UHFFFAOYSA-N 0.000 description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 239000012266 salt solution Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000010457 zeolite Substances 0.000 description 2
- 229910000570 Cupronickel Inorganic materials 0.000 description 1
- ILKBHIBYKSHTKQ-UHFFFAOYSA-N Diisopropylamine dichloroacetate Chemical compound OC(=O)C(Cl)Cl.CC(C)NC(C)C ILKBHIBYKSHTKQ-UHFFFAOYSA-N 0.000 description 1
- 238000006424 Flood reaction Methods 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- VVWYOYDLCMFIEM-UHFFFAOYSA-N Propantheline Chemical compound C1=CC=C2C(C(=O)OCC[N+](C)(C(C)C)C(C)C)C3=CC=CC=C3OC2=C1 VVWYOYDLCMFIEM-UHFFFAOYSA-N 0.000 description 1
- 229940072107 ascorbate Drugs 0.000 description 1
- 235000010323 ascorbic acid Nutrition 0.000 description 1
- 239000011668 ascorbic acid Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- YOCUPQPZWBBYIX-UHFFFAOYSA-N copper nickel Chemical compound [Ni].[Cu] YOCUPQPZWBBYIX-UHFFFAOYSA-N 0.000 description 1
- 229960004643 cupric oxide Drugs 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- AFZSMODLJJCVPP-UHFFFAOYSA-N dibenzothiazol-2-yl disulfide Chemical compound C1=CC=C2SC(SSC=3SC4=CC=CC=C4N=3)=NC2=C1 AFZSMODLJJCVPP-UHFFFAOYSA-N 0.000 description 1
- 229940084113 diisopropylamine dichloroacetate Drugs 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- ZZUFCTLCJUWOSV-UHFFFAOYSA-N furosemide Chemical compound C1=C(Cl)C(S(=O)(=O)N)=CC(C(O)=O)=C1NCC1=CC=CO1 ZZUFCTLCJUWOSV-UHFFFAOYSA-N 0.000 description 1
- 238000002309 gasification Methods 0.000 description 1
- 230000002363 herbicidal effect Effects 0.000 description 1
- 239000004009 herbicide Substances 0.000 description 1
- 229910000480 nickel oxide Inorganic materials 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- MUMZUERVLWJKNR-UHFFFAOYSA-N oxoplatinum Chemical compound [Pt]=O MUMZUERVLWJKNR-UHFFFAOYSA-N 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 229910003446 platinum oxide Inorganic materials 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- DURULFYMVIFBIR-UHFFFAOYSA-N practolol Chemical compound CC(C)NCC(O)COC1=CC=C(NC(C)=O)C=C1 DURULFYMVIFBIR-UHFFFAOYSA-N 0.000 description 1
- 229960001749 practolol Drugs 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 229960000697 propantheline Drugs 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000006273 synthetic pesticide Substances 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
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- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a supported catalyst used for synthesis of diisopropylamine from isopropylamine. Roasted gamma-alumina is used as a supporter, and active ingredients are supported on the supporter to obtain the supported catalyst, wherein the active ingredients consist of nickel, copper and platinum; the sum of weight of the nickel, the copper, the platinum and the roasted gamma-Al2O3 is referred to as total weight; the nickel accounts for 15-25 percent of the total weight; the copper accounts for 5-12 percent of the total weight; and the platinum accounts for 0.5-1 percent of the total weight. The invention also provides a preparation method of the supported catalyst. The invention also provides application of the supported catalyst, i.e., the supported catalyst is used for synthesizing the diisopropylamine from the isopropylamine. The supported catalyst provided by the invention is used in a process of disproportionation reaction of the isopropylamine for synthesizing the diisopropylamine. The supported catalyst has the characteristics of environmental friendliness, low toxicity, greatly reduced cost compared with other processes, suitability for industrial production and the like.
Description
Technical field
The present invention relates to loaded catalyst of the synthetic diisopropylamine of a kind of isopropylamine disproportionated reaction and its production and use.
Background technology
Diisopropylamine (Diisopropylamine), its molecular formula are C
6H
15N, its structural formula is as follows:
Diisopropylamine is a kind of important fine chemistry intermediate, be mainly used in synthetic pesticide, herbicide etc., secondly for the synthesis of medical diisopropyl amine dichloro acetate, diisopropylamine ascorbate, practolol and propantheline, in addition, also for the synthesis of dyestuff, thiofide, surfactant etc.
The report that synthesizes the catalyst of diisopropylamine about isopropylamine by disproportionated reaction in document mainly contains two kinds, is respectively K/H β zeolite-A l
2O
3Catalyst and ZrO
2/ H β zeolite-A l
2O
3Catalyst.Specific as follows:
1), patent CN1148341C has reported with K/H β zeolite-A l
2O
3For the synthetic diisopropylamine of catalyst isopropylamine, H β zeolite 50～95wt% wherein, potassium is 0.2～4.0wt%, surplus is γ-Al
2O
3Catalyst breakage is become 8～20 orders, get in a certain amount of stainless steel reactor of packing into, react for upper feeding, reactant flows out from reactor bottom, 200～300 ℃ of reaction temperatures, reaction pressure normal pressure～0.8MPa, air speed 0.2～1.5h
-1Obtain finally the conversion ratio 10～25% of isopropylamine, diisopropylamine selectively all more than 99%,, although this catalyst is selective good, make the conversion ratio of isopropylamine very low because catalytic activity is not high.
2), patent CN1127373C has reported with ZrO
2/ H β zeolite-A l
2O
3For catalyst, H β zeolite 20～90wt% wherein, zirconia is 2.0～15.0wt%, surplus is γ-Al
2O
3200～300 ℃ of reaction temperatures, pressure are normal pressure～0.8MPa, air speed 0.2～1.0h
-1This reaction isopropylamine conversion ratio with K/H β zeolite-A l
2O
3For the situation of catalyst similar, neither be very high, selectively will be slightly lower than K/H β zeolite-A l
2O
3Catalyst.In addition, use zr element in this catalyst, expensive more a lot of than copper nickel element commonly used on general industry, so this catalyst is difficult for heavy industrialization.
Summary of the invention
The technical problem to be solved in the present invention is to provide that a kind of activity is high, cost is low, selective high loaded catalyst that is used for the synthetic diisopropylamine of isopropylamine and preparation method thereof.
In order to solve the problems of the technologies described above, the invention provides a kind of loaded catalyst for the synthetic diisopropylamine of isopropylamine, take gama-alumina after roasting as carrier, load active component on carrier, obtain loaded catalyst; Active component is comprised of nickel, copper and platinum; γ-Al after nickel, copper, platinum and roasting
2O
3The weight sum be called gross weight, described nickel accounts for 15～25% of gross weight, copper accounts for 5～12% of gross weight, platinum accounts for 0.5～1% of gross weight.
After above-mentioned roasting, gama-alumina can be taked the following methods preparation: with gama-alumina (γ-Al
2O
3) prior to 400～500 ℃ of roasting 1.5～2.5h, then in 550～600 ℃ of roasting 4.5～5.5h; γ-Al after roasting
2O
3After testing: after this roasting, the specific area of gama-alumina is about 190～200m
2/ g, aperture is 15.0～15.8nm.Gama-alumina (γ-Al
2O
3) be common commercially available prod, its particle diameter is 2～3mm.The remarks explanation: after roasting, the particle diameter of gama-alumina is equal to the particle diameter of gama-alumina (before being roasting) substantially.
The present invention also provides the preparation method of above-mentioned loaded catalyst for the synthetic diisopropylamine of isopropylamine simultaneously, comprises the following steps:
1), biscuit firing:
With gama-alumina (γ-Al
2O
3) prior to 400～500 ℃ of roasting 1.5～2.5h, then in 550～600 ℃ of roasting 4.5～5.5h; γ-Al after roasting
2O
3
2), with step 1) γ-Al after the roasting of gained
2O
3With water retting at least 36 hours, then measure the volume that water reduces, thereby γ-Al after roasting
2O
3Pore volume density (that is, pore volume);
3), first dipping:
Nickel salt, mantoquita and platinum salt are dissolved in water (for example being distilled water), obtain mixed solution; With step 1) γ-Al after the roasting of gained
2O
3Impregnated in mixed solution γ-Al after roasting
2O
3Pore volume be 1/2～1.1/2 (the best is 1/2) of mixed liquor volume, dip time equals step 2) dip time; γ-Al after platinum in nickel in nickel salt, the copper in mantoquita, platinum salt and roasting
2O
3The weight sum be called gross weight, the nickel in nickel salt accounts for 15～25% of gross weight, the copper in mantoquita accounts for 5～12% of gross weight, the platinum in platinum salt accounts for 0.5～1% of gross weight;
After dipping finishes, filter, obtain filtrate and solid, solid is catalyst;
4), after baking:
With step 3) catalyst of gained is in 40～60 ℃ of dryings 1.5～2.5 hours (being preferably 50 ℃ of dryings 2 hours), then in 260～300 ℃ of roastings 5～7 hours (being preferably 280 ℃ of roastings 6 hours), more naturally is cooled to room temperature;
5), double-steeping:
With step 4) catalyst of gained puts into step 3) the filtrate dipping of gained is until filtrate is all absorbed (approximately 20～28h);
6), step 5) catalyst of gained is in 75～95 ℃ of dryings 1.5～2.5 hours (being preferably 85 ℃ of dryings 2 hours), then in 430～470 ℃ of roastings 5～7 hours, more naturally is cooled to room temperature; Must be used for the loaded catalyst by the synthetic diisopropylamine of isopropylamine.
Further improvement as the preparation method of the loaded catalyst for the synthetic diisopropylamine of isopropylamine of the present invention: nickel salt is nickel nitrate, and mantoquita is copper nitrate, and platinum salt is platinum nitrate.
The present invention also provides the method for utilizing the synthetic diisopropylamine of above-mentioned loaded catalyst simultaneously, carries out successively following steps:
1), loaded catalyst is activated, must activate back loading type catalyst; Activation back loading type catalyst is placed in fixed bed reactors;
2), will be placed in head tank as the isopropylamine of material liquid, utilize at the uniform velocity sample introduction of sampling pump, the material liquid vaporization is rear by containing the fixed bed reactors of activation back loading type catalyst, face hydrogen amine disproportionated reaction with the activation back loading type catalyst in fixed bed reactors, the volume space velocity of material liquid is 0.1～0.25h
-1, it is 0.7～1.1Mpa that the adjusting hydrogen pressure makes the pressure of fixed bed reactors, the fixed bed reaction actuator temperature is 200～240 ℃;
3), collect step 2) product of gained carries out atmospheric distillation, obtains diisopropylamine (collecting the cut of 84 ℃～86 ℃).
Improvement as the method for synthetic diisopropylamine of the present invention: loaded catalyst is activated and comprises the following steps step 1):
1), loaded catalyst is carried out primary activation, duration of ventilation, ventilation flow rate and heating-up temperature in different soak time sections during primary activation are as shown in table 1 below:
Table 1
2), the loaded catalyst after primary activation is being activated under the hydrogen effect again between 100～250 ℃, until evaporated condensation water produces; Must activate back loading type catalyst.
In the method for synthetic diisopropylamine of the present invention:
The remarks explanation: above-mentioned catalyst refers to loaded catalyst, and the stereomutation amount of loaded catalyst before and after activation almost do not have, and this very little variable can be ignored.
Be used for the synthetic diisopropylamine of isopropylamine disproportionated reaction after loaded catalyst activation of the present invention.During the synthetic diisopropylamine of isopropylamine disproportionated reaction, reaction is carried out under hydro condition, and reaction temperature is 200～240 ℃, reaction pressure 0.7～1.1MPa, and the volume space velocity of reactant (isopropylamine) is 0.1～0.25h
-1Volume space velocity=isopropylamine volume flow (m
3/ h)/catalyst volume (m
3).That is the copper on the catalyst that, uses in reaction, nickel, platinum have been simple substance.
In the present invention, loaded catalyst prepares gained (being that catalyzed dose of metal salt solution absorbs fully) by equi-volume impregnating, its process comprises the roasting of carrier, with aquametry pore volume density, the metal salt solution of preparation two volumes, 2 dippings of carrier and slaine, dry, roasting process.
Use loaded catalyst of the present invention in the process of the synthetic diisopropylamine of isopropylamine disproportionated reaction, have the following advantages:
(1), avoided the generation of water from source, thereby the appearance of having avoided a series of azeotropic relevant with water to form has alleviated the burden of separating greatly.
(2), this catalyst activity high, selectively good, cost is low.
(3), the preparation method of loaded catalyst of the present invention has the characteristics such as raw material sources are extensive, simple to operate; Use loaded catalyst of the present invention in the process of the synthetic diisopropylamine of isopropylamine disproportionated reaction, have environmental friendliness, toxicity low, compare cost with other techniques and greatly reduce, be applicable to the characteristics such as suitability for industrialized production.
Description of drawings
Below in conjunction with accompanying drawing, the specific embodiment of the present invention is described in further detail.
Fig. 1 is the schematic diagram of the present invention for the synthesis of the device of diisopropylamine.
The specific embodiment
The preparation method of embodiment 1, a kind of loaded catalyst for the synthetic diisopropylamine of isopropylamine, carry out following steps successively:
1), biscuit firing:
With commercially available γ-Al
2O
3(particle diameter is 2～3mm) to put into Muffle furnace at 400～500 ℃ of roasting 2h, then in 550～600 ℃ of roasting 5h; γ-Al after roasting
2O
3
After testing: γ-Al after roasting
2O
3Specific area be 190～200m
2/ g, aperture is 15.0～15.8nm, particle diameter remains unchanged substantially.
2), with step 1) γ-Al after the roasting of gained
2O
3With water retting 36 hours, then measure the volume that water reduces, the volume that water reduces is γ-Al after roasting
2O
3Pore volume; γ-Al after roasting
2O
3Pore volume density (being pore volume) be 0.9ml/g.
3), first dipping:
66.8g six water nickel nitrates, 27.8g nitrate trihydrate copper and 0.9g platinum nitrate are dissolved in distilled water, then water (for example for distilled water) is settled to 104.4mL, obtains mixed solution; With step 1) γ-Al after the roasting of gained
2O
358g impregnated in mixed solution and (that is, to make γ-Al after roasting
2O
3Pore volume be mixed liquor volume 1/2); Dip time is 36 hours;
After dipping finishes, filter, obtain filtrate and solid, solid is catalyst;
4), after baking:
With step 3) catalyst of gained is in 50 ℃ of dryings 2 hours, then in Muffle furnace in 280 ℃ of roastings 6 hours, more naturally be cooled to room temperature;
5), double-steeping:
With step 4) catalyst of gained puts into step 3) filtrate of gained floods 24h, this moment step 3) catalyzed dose of the filtrate of gained all absorbs.
6), step 5) catalyst of gained is in 85 ℃ of dryings 2 hours, then in Muffle furnace in 450 ℃ of roastings 6 hours, more naturally be cooled to room temperature; The loaded catalyst that must be used for the synthetic diisopropylamine of isopropylamine.
In this loaded catalyst, contained Ni, Cu and Pt are about respectively 17%, 9%, 0.6% (W/W) (with simple substance form, calculating).
Remarks explanation: γ-Al after roasting
2O
3Weight, the weight of nickel element in six water nickel nitrates, in nitrate trihydrate copper in the weight of copper and platinum nitrate the weight sum of platinum element be gross weight, copper, nickel, the weight of platinum element, respectively divided by gross weight, namely obtains above-mentioned three % by weight.
The production method of experiment 1, a kind of diisopropylamine, use device as shown in Figure 1, carries out successively following steps:
1), loaded catalyst is activated, comprise following 2 steps:
1., first carry out primary activation, during primary activation shown in duration of ventilation, ventilation flow rate and the heating-up temperature table 1 as mentioned in the above of different soak time sections; This step can be carried out outside fixed bed reactors, also can utilize fixed bed reactors (but need to add N
2Connecting pipe).
2., the loaded catalyst after primary activation is loaded in fixed bed reactors and again activates in 100～250 ℃ (being for example 150～200 ℃) under the hydrogen effect, until evaporated condensation water produces; Must activate back loading type catalyst.
At this moment, the cupric oxide in loaded catalyst, nickel oxide and platinum oxide all change into copper, nickel, platinum accordingly.
Certainly, above-mentioned activation processing also can be carried out elsewhere, then will activate rear catalyst and be packed in fixed bed reactors.
2), 355g (6mol) isopropylamine is placed in head tank as material liquid, utilize at the uniform velocity sample introduction of sampling pump, isopropylamine by the vaporizer that is arranged in the fixed bed reactors top after (effect of vaporizer be make isopropylamine gasification) face hydrogen amine disproportionated reaction (H with the activation back loading type catalyst (also can be described as beds) of fixed bed reactors
2By entering in fixed bed reactors after vaporizer), the volume space velocity of material liquid (isopropylamine) is 0.15h
-1It is 0.9Mpa that the adjusting hydrogen pressure makes the pressure in fixed bed reactors, and beds (that is, in fixed bed reactors) temperature is controlled to be 220 ℃, reacted product is collected with liquid form after the condensation of condenser, reaction is analyzed and carry out step 3 after finishing) atmospheric distillation.
3), the product that will collect carries out atmospheric distillation, the cut of collecting 33 ℃ is unreacted isopropylamine, can again recycle.The cut of collecting 84 ℃～86 ℃ is diisopropylamine, obtains product diisopropylamine 185.1g, and the conversion ratio of isopropylamine is 61.1%, and diisopropylamine is selectively 99.6%.
Products therefrom is correct through characterizing structure.
Change the volume space velocity of load capacity, reaction temperature, reaction pressure and the material liquid of copper nickel platinum on catalyst in experiment 1; All the other steps, with experiment 1, obtain respectively testing 2～experiment 21.The conversion ratio of the isopropylamine of gained and diisopropylamine selectively as shown in table 2.
Table 2
Annotate: the preparation method of the loaded catalyst of experiment 2～experiment 21, step 3 except embodiment 1) consumption of six water nickel nitrates, nitrate trihydrate copper and the platinum nitrate of first dipping carries out the correspondence change according to the copper content in table 2, nickel content, platinum content respectively, and all the other are all with embodiment 1.
Contrast test, the load capacity (as shown in table 3) of copper nickel platinum on catalyst in experiment 1 that change, all the other are with testing 1; Must contrast 1～contrast 5; Acquired results is as shown in table 3.
Table 3
Annotate: the preparation method of the loaded catalyst of contrast 1～contrast 5, step 3 except embodiment 1) consumption of six water nickel nitrates, nitrate trihydrate copper and the platinum nitrate of first dipping carries out the correspondence change according to the copper content in table 3, nickel content, platinum content respectively, and all the other are all with embodiment 1.
Finally, it is also to be noted that, what more than enumerate is only several specific embodiments of the present invention.Obviously, the invention is not restricted to above embodiment, many distortion can also be arranged.All distortion that those of ordinary skill in the art can directly derive or associate from content disclosed by the invention, all should think protection scope of the present invention.
Claims (5)
1. be used for the loaded catalyst of the synthetic diisopropylamine of isopropylamine, it is characterized in that: take gama-alumina after roasting as carrier, load active component on described carrier, obtain loaded catalyst; Described active component is comprised of nickel, copper and platinum; γ-Al after described nickel, copper, platinum and roasting
2O
3The weight sum be called gross weight, described nickel accounts for 15～25% of gross weight, copper accounts for 5～12% of gross weight, platinum accounts for 0.5～1% of gross weight.
2. the preparation method of the loaded catalyst for the synthetic diisopropylamine of isopropylamine as claimed in claim 1 is characterized in that comprising the following steps:
1), biscuit firing:
With gama-alumina prior to 400 ~ 500 ℃ of roasting 1.5 ~ 2.5h, then in 550 ~ 600 ℃ of roasting 4.5 ~ 5.5h; γ-Al after roasting
2O
3
2), with γ-Al after the roasting of step 1) gained
2O
3With water retting at least 36 hours, then measure the volume that water reduces, thereby γ-Al after roasting
2O
3Pore volume density;
3), first dipping:
Nickel salt, mantoquita and platinum salt are dissolved in the water, obtain mixed solution; With γ-Al after the roasting of step 1) gained
2O
3Impregnated in mixed solution γ-Al after described roasting
2O
3Pore volume be 1/2 ~ 1.1/2 of mixed liquor volume, dip time equals step 2) dip time; γ-Al after platinum in nickel in described nickel salt, the copper in mantoquita, platinum salt and roasting
2O
3The weight sum be called gross weight, the nickel in described nickel salt accounts for 15～25% of gross weight, the copper in mantoquita accounts for 5～12% of gross weight, the platinum in platinum salt accounts for 0.5～1% of gross weight;
After dipping finishes, filter, obtain filtrate and solid, described solid is catalyst;
4), after baking:
The catalyst of step 3) gained, in 40 ~ 60 ℃ of dryings 1.5 ~ 2.5 hours, then in 260 ~ 300 ℃ of roastings 5 ~ 7 hours, then is cooled to room temperature naturally;
5), double-steeping:
The filtrate of the catalyst of step 4) gained being put into the step 3) gained is flooded until filtrate is all absorbed;
6), the catalyst of step 5) gained is in 75 ~ 95 ℃ of dryings 1.5 ~ 2.5 hours, then in 430 ~ 470 ℃ of roastings 5 ~ 7 hours, more naturally is cooled to room temperature; Must be used for the loaded catalyst by the synthetic diisopropylamine of isopropylamine.
3. the preparation method of the loaded catalyst for the synthetic diisopropylamine of isopropylamine according to claim 2, it is characterized in that: described nickel salt is nickel nitrate, and mantoquita is copper nitrate, and platinum salt is platinum nitrate.
4. utilize the method for the synthetic diisopropylamine of loaded catalyst as claimed in claim 1, it is characterized in that: carry out successively following steps:
1), loaded catalyst is activated, must activate back loading type catalyst; Activation back loading type catalyst is placed in fixed bed reactors;
2), will be placed in head tank as the isopropylamine of material liquid, utilize at the uniform velocity sample introduction of sampling pump, the material liquid vaporization is rear by containing the fixed bed reactors of activation back loading type catalyst, face hydrogen amine disproportionated reaction with the activation back loading type catalyst in fixed bed reactors, the volume space velocity of material liquid is 0.1 ~ 0.25h
-1, it is 0.7 ~ 1.1Mpa that the adjusting hydrogen pressure makes the pressure of fixed bed reactors, the fixed bed reaction actuator temperature is 200 ~ 240 ℃;
3), collect step 2) product of gained carries out atmospheric distillation, obtains diisopropylamine.
5. the method for synthetic diisopropylamine according to claim 4 is characterized in that: step 1) loaded catalyst is activated and comprises the following steps:
1), loaded catalyst is carried out primary activation, the time of primary activation adds up to 24h, carries out successively the described time period of following table; Duration of ventilation, ventilation flow rate and heating-up temperature in different soak time sections during described primary activation are as shown in the table:
2), the loaded catalyst after primary activation is activated again in 100～250 ℃ under the hydrogen effect, until evaporated condensation water produces; Must activate back loading type catalyst.
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| CN103787892B (en) * | 2012-11-01 | 2016-01-20 | 中国石油化工股份有限公司 | A kind of method of Isopropylamine synthesis Diisopropylamine |
| CN108187679A (en) * | 2017-12-28 | 2018-06-22 | 之江（四川）高新材料应用技术研究院有限公司 | Synthesize the method and used catalyst of 1,4- lupetazins |
| CN110152714B (en) * | 2018-03-20 | 2022-04-01 | 浙江建业化工股份有限公司 | Catalyst for producing isobutylamine and diisobutylamine and use method thereof |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| ES2055855T3 (en) * | 1989-12-23 | 1994-09-01 | Hoechst Ag | PROCEDURE FOR THE MANUFACTURE OF N, N-DIMETHYLAMINES. |
| CN1785514A (en) * | 2005-11-08 | 2006-06-14 | 浙江建德建业有机化工有限公司 | Catalyst for preparing n-propylamine, its preparation method and application |
| JP3800632B2 (en) * | 1994-05-31 | 2006-07-26 | 東ソー株式会社 | Amination catalyst and process for producing aliphatic amines using the same |
| CN101111468A (en) * | 2005-02-01 | 2008-01-23 | 巴斯福股份公司 | Method for producing bis-[(3-dimethylamino)propyl]amine (dipropylene triamine, dpta) |
| WO2008156320A1 (en) * | 2007-06-19 | 2008-12-24 | Postech Academy-Industry Foundation | Magnetic nanocatalyst composition and method for the preparation thereof |
| CN101880236A (en) * | 2009-05-08 | 2010-11-10 | 中国石油化工股份有限公司 | Method for synthesizing isopropamide |
| JP4641497B2 (en) * | 2005-12-28 | 2011-03-02 | 花王株式会社 | Aliphatic alcohol amination catalyst and method for producing amine using the catalyst |
| CN102188975A (en) * | 2011-03-09 | 2011-09-21 | 浙江工业大学 | Loaded nickel-base bi-component catalyst and application thereof |
| CN102336672A (en) * | 2011-09-21 | 2012-02-01 | 浙江建业化工股份有限公司 | Method for producing isoamyl amine |
-
2012
- 2012-03-04 CN CN2012100545324A patent/CN102614894B/en active Active
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| ES2055855T3 (en) * | 1989-12-23 | 1994-09-01 | Hoechst Ag | PROCEDURE FOR THE MANUFACTURE OF N, N-DIMETHYLAMINES. |
| JP3800632B2 (en) * | 1994-05-31 | 2006-07-26 | 東ソー株式会社 | Amination catalyst and process for producing aliphatic amines using the same |
| CN101111468A (en) * | 2005-02-01 | 2008-01-23 | 巴斯福股份公司 | Method for producing bis-[(3-dimethylamino)propyl]amine (dipropylene triamine, dpta) |
| CN1785514A (en) * | 2005-11-08 | 2006-06-14 | 浙江建德建业有机化工有限公司 | Catalyst for preparing n-propylamine, its preparation method and application |
| JP4641497B2 (en) * | 2005-12-28 | 2011-03-02 | 花王株式会社 | Aliphatic alcohol amination catalyst and method for producing amine using the catalyst |
| WO2008156320A1 (en) * | 2007-06-19 | 2008-12-24 | Postech Academy-Industry Foundation | Magnetic nanocatalyst composition and method for the preparation thereof |
| CN101880236A (en) * | 2009-05-08 | 2010-11-10 | 中国石油化工股份有限公司 | Method for synthesizing isopropamide |
| CN102188975A (en) * | 2011-03-09 | 2011-09-21 | 浙江工业大学 | Loaded nickel-base bi-component catalyst and application thereof |
| CN102336672A (en) * | 2011-09-21 | 2012-02-01 | 浙江建业化工股份有限公司 | Method for producing isoamyl amine |
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